Monoazo dyestuffs containing a carboxamido-4(3h)-quinazolone group

ABSTRACT

COMPOUNDS OF THE FORMULAE:   1-((2-R3,3-R4,4-R5,5-R6,6-R7-PHENYL)-N=N-),2-(HO-),3-   ((2-R2,R8,R9,R10-3,4-DIHYDROQUINAZOLIN-4-ONYL)-NH-CO-)   NAPHTHALENE   1-((2-R3,3-R4,4-R5,5-R6,6-R7-PHENYL)-N=N-),2-(HO-),3-   ((2-R2,R8,R9,R10-3,4-DIHYDROQUINAZOLIN-4-ONYL)-NH-CO-)   CARBAZOLE   1-((2-R3,3-R4,4-R5,5-R6,6-R7-PHENYL)-N=N-),2-(HO-),3-   ((2-R2,R8,R9,R10-3,4-DIHYDROQUINAZOLIN-4-ONYL)-NH-CO-)   DIBENZOFURAN   WHEREIN R2 IS HYDROGEN, C1-C4 ALKYL, C1-C4 ALKOXY (FOR SECOND AND THIRD FORMULAE ONLY), PHENYL, BENZYL OR METHYL-, METHOXY- OR CHLORINE- SUBSTITUTED BENZYL, EACH OF R3, R4, R5, R6 AND R7 IS HYDROGEN, CHLORINE, BROMINE, C1-C4 ALKYL, C1-C4 ALKOXY, NITRO, CYANO, TRIFLUOROMETHHYL, C1-C4 ALKOXYCARBONYL, C1-C4 ALKYLSULFONYL, PHENYLSULFONYL, UREIDO, CARBAMOYL, N-C1-C4 ALKYLCARBAMOYL, NPHENYLCARBAMOYL, SULFAMOYL, N-C1-C4 ALKYLSULFAMOYL, N-PHENYLSULFAMOYL, ACETYL, PROPIONYL, BUTYRYL, PHENYLACETYL, BENZOYL, ACETYLAMINO, PROPIONYLAMINO, BUTYRYLAMINO, PHENYLACETYLAMINO OR BENZOYLAMINO, AND EACH OF R8, R9 AND 10 IS HYDROGEN, CHLORINE, BROMINE, C1-C4 ALKYL OR C1-C4 ALKOXY, ARE PROVIDED, WHICH ARE USEFUL AS WATER INSOLUBLE DYSTUFFS CHARACTERIZED BY HIGH FASTNESS TO SOLVENTS, MIGRATION AND LIGHT.

United States Patent 3,719,657 MONOAZO DYESTUFFS CONTAINING A CARBOX- AM'IDO-4(3H)-QUINAZOLONE GROUP Kinjiro Hama, Nishinomiya, Nobuo Mishima, Hirakata, and Kazuo Miyamoto, Takarazuka, Japan, assignors to Sumitomo Chemical C0., Ltd. No Drawing. Filed Jan. 12, 1970, Ser. No. 2,405 Claims priority, application Japan, Jan. 17, 1969,

4/ 3,704 Int. Cl. (30% 29/36, 43/12 US. Cl. 260-154 9 Claims ABSTRACT OF THE DISCLOSURE Compounds of the formulae:

wherein R is hydrogen, C C alkyl, C -C alkoxy (for second and third formulae only), phenyl, benzyl or methyl, methoxyor chlorinesubstituted benzyl, each of R R R R and R is hydrogen, chlorine, bromine,

C -C alkyl, C -C alkoxy, nitro, cyano, trifluoromethyl,

C -C alkoxycarbonyl, C -C alkylsulfonyl, phenylsulfonyl, ureido, carbamoyl, N-C C alkylcarbarnoyl, N- phenylcarbamoyl, sulfamoyl, N-C C alkylsulfamoyl, N-phenylsulfamoyl, acetyl, propionyl, butyryl, phenylacetyl, benzoyl, acetylamino, propionylamino, butyrylamino, phenylacetylamino or benzoylamino, and each of R R and R is hydrogen, chlorine, bromine, C -C alkyl or C -C alkoxy, are provided, which are useful as water insoluble dyestuffs characterized by high fastness to solvents, migration and light.

This invention relates to novel water-insoluble monoazo dyestuifs represented by the general Formula I:

3,719,657 Patented Mar. 6, 1973 "ice wherein A is a benzene nucleus which may be substituted by groups which do not impart solubility in water, the benzene nucleus B may be substituted by groups which do not impart solubility in water, R represents a naphthalene residue in which an azo group, hydroxyl group and carbamoyl group are bonded respectively in the 1-, 2- and 3-positions, carbazol residue in which they are bonded respectively in the 1-, 2- and 3-positions or diphenylene oxide residue in which they are bonded respectively in 4-, 3- and 2-positions and R represents hydrogen atom, alkoxy, alkyl, aryl or aralkyl group (the aryl may be substituted by groups which do not impart solubility in water). In the present invention, the alkyl and alkoxy mean alkyl and alkoxy having 1 to 4 carbon atoms.

This invention also relates to a process for the manufacture of these dyestuffs.

More particularly the present invention relates to waterinsoluble monoazo dyestuffs represented by the general Formula II, III or IV:

wherein A, the benzene nucleus B and R are as defined before.

These dyestuffs are prepared according to this invention by coupling a diazotised primary amine of the benzene series which may be substituted by groups which do not impart solubility in Water with, as an azo component, an aromatic or heterocyclic o-oxycarboyl compound of amino-4(3H)-quinazolone represented by the following general Formula V, VI or VII:

CO-NH H CONH (JO-NH 0H CONH N: -12, Hr

Q (VI) CO-NH 0H GONE OH COX (VIII) OH C OX 0 G O N wherein A is as defined before and X represents a halogen atom, with an amino-4(3H)-q-uinazolone represented by the general Formula XI:

0 O-NH wherein R and the benzene nucleus B are as defined before.

As for the primary amine of the benzene series to be used in the process of the present invention, the following formula may be given,

It, I.

wherein each of R R R R and R is hydrogen, a halogen, an alkyl, an alkoxy, nitro, cyano, trifluoromethyl, an alkoxycarbonyl, an alkylsulfonyl, an arylsulfonyl, ureido, carbamoyl, an N-alkylcarbamoyl, an N-arylcarbamoyl, sulfamoyl, an N-alkylsulfamoyl, an N-arylsulfamoyl, an acyl, an aroyl, an acylamino or an aroylamino, in which each aryl may be substituted by groups which do not impart solubility in water.

As for the primary amines, there may be mentioned, for example,

amino-benzene, 1-amin0-2-chlorobenzene, l-amino-Z-fluorobenzene, 1-amino-3-bromobenzene, 1-amino-3-iodobenzene, 1-amino-4-chlorobenze'ne, 1-amino-2-methy1benzene, 1-amino-2-methoxybenzene, 1-amino-4-methylbenzene, 1-amino-4-methoxybenzene, 1-amino-2-nitrobenzene, l-aminobenzene-Z-carboxylic acid methyl ester, 1-amin0-2,4-dimethylbenzene, l-amino-Z,S-dimethoxybenzene, 1-amino-2-rnethyl-4-chlorobenzene, 1-amino-2-methyl-5-chlorobenzene, l-amino-2-methyl-4-nitrobenzene, l-amino-Z-methoxy-4-chlorobenzene, 1-amino-2-methoxy-S-chlorobenzene, 1-amino-2-methoXy-4-nitrobenzene, 1-amino-2-nitro-4-methylbenzene, 1-amino-2-nitro-4-methoxybenzene, 1-amino-2,5-dichlorobenzene, 2-amino-4,4'-dichlorodiphenyl ether, 1-amino-2,4,5-trichlorobenzene, 3-amin0-benzoic acid amide, 3-amino-4-methoxy-benzoic acid amide, 3-amino-benzoic acid methyl amide, 3-amino-benzoic acid anilide, 3-amino-4-meth0xy-benzoic acid anilide, 3-amino-4-methoxy-benzoic acid-2-methyl-3-chloranilide, 4-amino-benzoic acid amide, 1-amino-2-rnethoXy-5-sulfonic acid amide, 1-amino-2-methoxy-5-sulfonic acid anilide, 2-cyano-4-nitroaniline, 3-trifiuorornethylaniline, 4-amino-acetophenon, 3-amino-4-chloro-phenylurea, 3-amino-4-chloro-diphenylsulfon, Z-methoxy-S-ethylsulfonylaniline, 2-chloro-4-acetylaminoaniline and 2-chloro-4(2-chloro)benzoylamino-aniline.

In order to manufacture the water-insoluble dyestuifs of the present invention the above mentioned amines may be diazotised in the usual manner and then coupled with an aromatic or heterocyclic o-oxycarboyl compound of amino-4(3H)-quinazolone having the Formula V, VI or VIII, preferably in the presence of a dispersing agent such as a nonionic active agent, an anionic active agent or a cationic active agent in an alkaline, neutral or acid medium, preferably in a neutral or a weak acid aqueous medium. The coupling reaction may be conducted in a proper organic solvent such as, for example, dimethylformamide, pyridine or methanol.

9 6-amino-2-(4'-rnethylphenyl)-4(3H)-quinazolone, 6-amino-2-benzyl-4 3H -quinazolone, and -amino-2-benzyl-4(3H) -quinazolone.

The treatment of the azocarboxylic acid with the halogenating agent is advantageously carried out in an inert solvent such as monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene or nitrobenzene. It is preferable to add dimenthylformamide thereto. Further, the condensation is carried out advantageously in an anhydrous medium. Under such conditions, generally, the reaction is carried out very easily at a temperature within the boiling point range of such ordinary organic solvents as, for example, toluene, monochlorobenzene, dichlorobenzene, trichlorobenzene and nitrobenzene. In order to accelerate this reaction, it is preferable to employ an acid-binding agent, for example, anhydrous sodium acetate or pyridine.

Thus, the insoluble dyestulf of the present invention is obtained at a high yield and in a pure state. However, in order to obtain a particularly pure fast dyeing, it is preferable to purify the dyestutf with the use of a proper solvent such as, for example, pyridine or dimethylformamide, in some cases, under heating.

The novel dyestuifs obtained by the present invention are water-insoluble and are characterized by having a very high fastness to solvents, migration and light. The dyestuffs of the invention can be used for the production of printing inks, lacquers and paints and further for coloring rubbers, natural resins and synthetic resins, coloring spun substances and dyeing and printing fabrics and paper by an ordinary pigment printing or dyeing process.

The present invention will be illustrated by the following examples in which all parts and percentages are by Weight unless otherwise specified.

EXAMPLE 1 16.6 parts of 3-amino-4-methoxybenzoic acid amide is dissolved in 250 parts of ice water and 94 parts of 35 hydrochloric acid and are diazotised with the addition of 23.2 parts of a 30% sodium nitrite solution. Apart from the above, 34.5 parts of 6-(2',2-oxynaphthoylamino)-2- methyl-4(3H)-quinazolone is dissolved in 30 parts of a 40% sodium hydroxide solution, 250 parts of water and 200 parts of methanol. Then 20 parts of a 5%aqueous solution of a dispersing agent (a reaction product of 1 mol of oleyl alcohol and 30 mols of ethylene oxide) is further added thereto. This solution is then poured to gether with the diazo solution during 30 minutes with severe stirring into a solution consisting of 400 parts of water, 12 parts of glacial acetic acid, 100 parts of a 30% sodium acetate solution and 20 parts of a 5% solution of the above mentioned dispersing agent. When the solution is stirred for 30 minutes after pouring, the coupling is completed. It is further stirred at 90 to 95 C. for 30 minutes and filtered to separate crystals, which are washed with water and dried at 60 C. The obtained product is treated with 400 parts of dimethylformamide at the boiling temperature for 2 hours and the mixture is cooled and filtered to separate crystals, which are washed with methanol and dried. There is obtained a clear bluish red water-insoluble dyestuif having the below mentioned structural formula, high in tinctorial strength and having a very high fastness to solvents, light and migration:

10 EXAMPLE 2 16.6 parts of 3-amino-4-methoxybenzoic acid amide is dissolved in 250 parts of ice water and 94 parts of 35% hydrochloric acid and is diazotised with the addition of 232 parts of a 30% sodium nitrite solution. Separately, 33.1 parts of 6-(2,3-oxynaphthoylarnino)-4(3H)-quinazolone is dissolved in 30 parts of a 40% sodium hydroxide solution and 400 parts of water. Then 20 parts of a 5% aqueous solution of a dispersing agent (a reaction product of 1 mol of oleyl alcohol and 30 mols of ethylene oxide) is further added thereto. The resulting solution is then poured together with the diazo solution during 30 minutes with severe stirring into a solution consisting of 400 parts of water, 12 parts of glacial acetic acid, 100 parts of a 30% sodium acetate solution and 20 parts of a 5% solution of the above mentioned dispersing agent. After pouring, the solution is stirred for30 minutes and filtered to separate crystals, which are washed with water and dried at 60 C. When the obtained product is treated with 350 parts of dimethylformamide at the boiling temperature for 2 hours and the mixture is cooled and then filtered to separate crystals, which are washed with methanol and dried, there is obtained a clear 'red water-insoluble dyestufi having the below mentioned structural formula and having a high fastness to solvents, light and migration:

EXAMPLE 3 A diazo solution is prepared by the process mentioned in Example 1 from 16.6 parts of 3-arnino-4-methoxybenzoic acid amide. Separately, 40.7 parts of 6-(2,3- oxynaphthoylamino)-2-pheny1-4 (3H) -quinazoline is dis solved in 30 parts of 40% sodium hydroxide solution, 200 parts of water and 200 parts of methane. Then 20 parts of a 5% aqueous solution of a dispersing agent (a reaction product of 1 mol of oleyl alcohol and 30 mols of ethylene oxide) is further added thereto. The resulting solution is then poured together with the diazo solution during 30 minutes with severe stirring into a solution consisting of 450 parts of water, 12 parts of glacial acetic acid, 100 parts of a 30% sodium acetate solution and 20 parts of a 5% solution of the above mentioned dispersing agent. After pouring, the solution is stirred for 30 minutes and is further stirred at to C. for 30 minutes.

It is then filtered to separate crystals which are washed with water, and dried at 60 C. to obtain a red waterinsoluble dyestuff. When it is treated with 400 parts of dimethylformamide at the boiling temperature for 2 hours, and the mixture is cooled and then filtered, to separate crystals, which are washed with methanol and dried, there is obtained a red water-insoluble dyestuff having the below mentioned structural formula, soft in grains and having a high fastness to migration, solvents and light:

EXAMPLES 4-44 Table 1 indicates combinations of some diazo components and azo components which are used to obtain waterinsoluble dyestuif having the same favorable fastness when coupled by the process mentioned in the above described examples.

TABLE 1 No. Diazo component I Azo components Aminob enzene- Red. Yellowish red.

6 (2-oxycarbazole-3-carboylamino)-4(3H)-quinazolo Yellowish brown. 6-(3'-oxydiphenylene oxide-2-earboylamino)4(3H)-qu1 rown.

7-(2' ,3-oxynaphthoylamino)4(311) -quinazolone gegowish red do e 8-(2,3-oxynaphthoy1arnino)-4(3H)-quinazolone Red. 7-(2,3-oxynapht hoylamino)-6-eh1oro-4(3H) -quinazolone Red. 7-(2-oxyearbazo1e-3-carboylamino) -6-ehloro-4(3H)-quinazolone Brown. 7-(2,3-oxynaphthoylarnino)-8-methoxy4(3H)-quinazo1one Bluish red. 7-(2,3-oxynaphthoylamin0)fi-methyl-4(3H) -quinazolone Red. 7-(3mxydiphenylene oxide-2'carboylamino)-6-methyl-4(3H)-quinazolone Brown. 6-(2 ,3-oxynaphthoylamino) -2-methyl4 (3H)-quinazolone Red. 6-(2,8'-oxynaphthoylamino) 2-methoxy-4(3H) -quinazolone Bordeaux. 6-(2-oxyearbazole-3-carboylamino) -2-met hyl-4 (3H)-quinaz olone Reddish brown. 6-(3-oxydipheny1ene oxide-2-earboylamino) -2-methyl-4 (3H)-quinazolone Do. do 7-(2,3-oxynaphthoy1amino)-2-methy1-4(3H)-quinazolone Bluish red. 1-amino-2methyl+ohlorobenzene 7-(2,3-oxynaphthoy1amino) -2-methoxy-4(3H) -quinazolone Red. do 6-(2,3-oxynaphthoylarnino) 7-bromo-2-methyl-4(3H)-quinazolone Red. do 7-(2,3-oxynaphthoylam1no)-6-ehloro-2-methyl-4(3H)-qu1nazolone Red. 3-amino4-rnethoxy-benzoie aeid anilide 6-(2,3-oxynahthoy1amino)-7-ehloro-2-methyl-4(3H)-quinazolone Red. do 8-(2,3-oxynaphthoylarnino) -6-chl0ro-2-methyl-4(3H) -quinazolone Red.

7 -(2 ,3 -oxynaphthoylamino) -6-methoxy-2-methyl-4(3H) -quinazolone. Bordeaux. 7-(2',3-oxynaphthoylarnino)-8-methoxy-2methy1-4(3H)-quinazolone Do. 8-(2,3'-oxynaphthoylamino)-2,G-dimethyHGH)-quinazolene Bluish red. 6-(2 -oxynaphthoylamino) -2-phenyl-4(3H)-quinazolone R dDo. o e 6-(2-oxyearbazole-3-carboylarnino) -2-phenyl-4(3H)-quinazolone Brown 6-(3-oxydiphenylene oxide-2-earboylarnino) -2-phenyl-4(3H) -quinazolone Do. 7-(2,3-oxynaphthoylamino)-2-phenyl-4(3H)-quinazolone Red. 7-(2-oxycarbazole-3-carboylamino)-2-phenyl-4(3H)-quinazo1one Brown. 6-(2,3-oxynaphthoylamino)-7-bromo-2-phenyl-4(3H)-quinazo1one Red. 37 do 6-(l3-oxydiphenylene oxide-2-carboylarnino) -7-bromo-2-pheny1-4(3H)-quinazo- Brown.

one. 33 do 6-(2,3-oxynaphthoylamino)-7-ehloro-2- henyl-4(3H)- uinazolone Red. 39 do 8-(2,3-oxynaphthoylamino)-6-chloro-2-phenyl-4(3H)-quinazo1one e 40 7-(2 ,3oxynaphthoylam ino) -6-methoxy-2-phenyl-4 (3H) -quinazolone Bluish red. 41 6-(2,3-oxynaphthoylam no)-2-(4-chlorophenyl)-4(3H)-quinazolone Red. 42 6-(2,3-oxynaphthoylamrno)-2-(4-methoxyphenyl)-4(3H)-quinazolone Bordeaux.

6-(2,3-oxynaphthoylamino)-2-(4-methylphenyl)-4(3H)-quino.zolone Bluish red. 6-(2,3-oxynaphthoylam1no)-2-benzyl-4(3H)-quinazolone Red.

EXAMPLE 45 33.4 parts of thronyl chloride is gradually added thereto r at the room temperature. The mixture is heated to Q i gg 1 555 82j gi iiii i gg aig g gfigg gg C. and stirred unt1l the generatlon of hydrochloric acid acid is suspended in 400 parts of o-dichlorobenzene, and Ceases' Then the temperature 18 l wered to 20 C. and

the precipitated crystals are separated by filtration, 16.7 parts of thronyl chloride is gradually added thereto o at the room temperature. The mixture is stirred at 100 C. ashed wlth benzene and dned at 60 under a reduced pressure. 33.25 parts of the thus obtained acid chloride f ii g gg gggggg gggflggg z ii z excess is stirred together with 400 parts of o-dichlorobenzene thionyl chloride hydrogen chloride and sulfur dioxide and 20 partso of anhydrous. pynd.me and the mlgiture 1S heated to 80 C. To thls mixture is added a solution preare removed under a reduced pressure. To this solution is ared b I i 23 7 t f 6 h n added a solution prepared by dissolving 17.3 parts of p lssovng. Pars O p e y 6 amino 2 methy1 4(3H) quinazo10ne in 200 parts of 4(3H)-qu1nazolone in 200 parts of o-dichlorobenzene dichlorobenzene and 70 parts of anhydrous pyridine. and parts of anhydroous pyndme and the mlxture ls Then the mixture is kept at 120 to 125 C. for about then kept at to 125 for oabout 15 hours h 15 hours. The temperature is then lowered and the rethe temPerature 1S lowered the rimming suiting red product is separated by filtration, washed Product 13 Separated filtratlon Wahed with o'dlchlorowith o-dichlorobenzene at 60 C. until the filtrate is no 50 benzene at the filtrat? Is no fi colorefi longer colored, then Washed with methanol and dried at then Washed W methanol and at 60 to obtain 60 C. There is obtainew a bluish red water-insoluble red Water-Insoluble dyestufi h.avmg the below dyestufi? having the below mentioned structural formula, i struqura} formula and havmg favorable fastness high in tinctorial strength and excellent in fastness to to hght mlgrtlon and solvents: solvent, light and migration: 55

0H, 0H GONE-- =(|1 N0: 011 CIIONH ME 2 me Q EXAMPLE 46 70.2 parts of a dyestuif obtained by coupling diazotised 1-arnino-2-nitro-4-methy1benzene with 2,3-oxynaphthoic Table 2 shows additional examples which were con- EXAMPLES 47-93 acid are suspended in 90.0 parts of chlorobenzene, and ducted in the same manner as that described above.

TABLE 2 N o. Diazo component Azo component Condensed amine Tint 1-amino-4-methylbenzene 2,3-oxynaphthoie acid 5-amin0-4(3H)-quinazo1one Red. do do 6-amino-4(3H)-quinazolone Red. -amin o .d0 Red.

do. 2-oxyoarbazole-3-earboxylic ae Brown do 3-oxydiphenylene oxide-2-carboxylic acid --do D do- 2,3-oxynaphthoie acid Red.

53 do do 8-ammo-4t3H -quinazolone D0.

2. A compound according to claim 1, namely 7. A compound according to claim 1, namely l 5 0 H OCH HO C ONH I a I Q gwN -N=N- I l-0H- 00m H0 CONE-Q11 HZNOC 1 I I N=N 3. A compound according to clarm 1, namely Q Q 1 f Hs z zS g 1 111 15 OCH; H0 OONH--N 8. A compound according to claim 1, namely 4. A compound according to claim 1, namely 0 H I (Hie-15 OCH HO CONH i i I 1 0011, H0 CONE-Q11 H2N0c OCH; H0 0 ONE-Gil- Q 6. A compound according to claim 1, namely 0 H I 0011, H0 CONE- 01 HO CONE-Q41 l I References Cited UNITED STATES PATENTS 3,118,870 1/1964 Dietz ct a1 26 0154 3,079,374 2/1963 Straley ct a1. 260 -152 3,086,004 4/1963 Gross et a1 260152 X 3,113,938 12/1963 'Nakaten et a1. 260154 X 1,012,055 12/1911 BOgert 260154 2,364,351 12/1944 Dickey 260--154 2,908,678 10/1959 Gocbel et al. 260154 3,154,532 10/1964 Weidinger et al 260-l54 3,157,631 11/1964 Wcidinger ct a1. 260154 OTHER REFERENCES Ciba, Chemical Abstracts, vol. 58, 9267-9268 (1963). Giuseppe, Chemical Abstracts, vol. 71, p. (1969).

FLOYD D. HIGEL, Primary Examiner US. Cl. X.R.

l0623, 288 Q; 1l7--138.8 R, 139, 154; 260152, 164, 203, 204, 256.4 Q 

